This invention is concerned with suppressing the deposition of corrosion products on fuel elements and other surfaces in the core of water-cooled nuclear power reactors.
Water-cooled nuclear power reactors have piping and components made of structurally strong materials. However, at least part of these materials continuously release by slow corrosion small amounts of metals to the hot water flowing over them. Common structural materials behaving in this way are carbon steels, stainless steels, and special Fe-Ni-Cr alloys such as Inconel-600 and Incoloy-800 (trademark). All these materials are normally used out-reactor, away from the neutron flux in the reactor core.
Zirconium alloys are used extensively in the core of water-cooled reactors because the atoms in zirconium are highly transparent to neutrons. However, some zirconium atoms do become radioactive. Fortunately, the zirconium alloys used for fuel sheathing of the UO.sub.2 fuel pellets (and for the pressure tubes in CANDU reactors) do not release their corrosion products to the water in detectable amounts.
The out-reactor structural materials release elements such as Fe, Ni, Cr and Co. These metals appear as dissolved ions in the water and as 0.1-1 .mu.m size particles. The metals may or may not be oxidized, partly depending on which phases are thermodynamically stable. In CANDU pressurized water reactors, iron is the major constituent in suspended particles in the coolant circuit, and the iron is present substantially as magnetite (Fe.sub.3 O.sub.4). As well, iron is probably the major dissolved metal in the water.
Some of these corrosion product atoms do become radioactive just by being carried through the reactor core by the water. However, to account for the quantity of radionuclides (radioactive atoms) observed in the primary circuit of a reactor, the corrosion products must spend a longer time in the neutron flux. This is possible by forming a deposit on in-reactor surfaces which may then release deposited atoms days later. The deposit may form in two ways; by particle deposition or by crystal growth of a metal or its oxide from solution. The small particles of corrosion products are known to deposit from turbulent water on all circuit surfaces. If crystal growth is not also occuring, then the deposited particles slowly dissolve. These deposits are very light (usually &lt;1 g metals/m.sup.2), so there are few atoms in the deposit to become radioactive. The deposit atoms are thought to be chiefly released by dissolution. The dissolved radioactive atoms deposit on all surfaces, so the out-reactor surfaces have a field of gamma radiation around them. Calculations show that the faster the deposited particles are dissolved, the fewer radionuclides are produced. Therefore, the deposits should be encouraged to dissolve.
Deposit formation by crystal growth is less common, but can usually be deduced from the crystalline appearance of the deposit, and from the large deposit weight (usually &gt;10 g metals/m.sup.2). A large inventory of radionuclides can accumulate in-reactor in these deposits. This is undesirable because deposit release would cause rapid growth of radiation fields out-reactor.
Reactors may operate with a direct or indirect cycle. Of primary concern here is a pressurized water reactor which must use the indirect cycle, but permits boiling to occur to a small degree in the reactor core. Both the pressure vessel (PWR) and pressure tube (CANDU PHWR) reactors can operate with some boiling.
In PWRs and PHWRs, the primary coolant usually has at least two deliberate additives: one additive to control the water pH, and another additive to combine with radiolytically-produced oxygen. Alkali metals (Li, Na, K) as hydroxides have been used to control the water pH in both PWRs and PHWRs, and so has ammonium hydroxide (NH.sub.4 OH). Hydrogen (or deuterium) gas is used to suppress radiolytic oxygen.
Boiling can concentrate alkali metal ions at the fuel sheaths. Any crevices which exist because of heavy deposits of corrosion products or because of the fuel sheath design (presence of appendages) can further promote high concentration differences between the bulk water and the water at the sheath surface, since the turbulent water cannot easily penetrate to flush the crevices. If the water pH exceeds pH 13 (at 25.degree. C.), zirconium alloys corrode rapidly and fuel sheaths can be penetrated. Another disadvantage of alkali metals is that some alkali metals become radioactive in the neutron flux and increase radiation fields around the primary circuit. In addition lithium-6 produces tritium in the neutron flux. Tritium causes internal radiation exposure when inhaled or absorbed by humans.
Ammonium hydroxide cannot be concentrated to the same degree by boiling (as can the alkali metals) because ammonia is much more volatile and transfers to the steam bubbles. Therefore, ammonium hydroxide is a more desirable pH additive than are the alkali metals if crevice corrosion of in-reactor materials is likely. As well, ammonium hydroxide suppresses radiolytic oxygen too, so it serves a dual purpose. Heretofore ammonia has been used for pH control (corrosion prevention), and radiolytic oxygen suppression in nuclear reactor aqueous coolants, in concentrations below about 60 mg NH.sub.3 /kg water (usually 5-25 mg NH.sub.3 /kg). See Canadian Pat. No. 823,849 Rae et al., and U.S. Pat. No. 3,294,644 Walton.
Recently, it has been observed that, with ammonia concentrations in the range normally advocated, in a closed cycle primary coolant with some boiling occurring, heavy deposits accumulate on surfaces in the core of the reactor, particularly on fuel element sheaths. These deposits may restrict heat transfer and cause fuel sheath failure. The deposits raise the pressure loss of water pumped through the core, and contain a large quantity of radionuclides which if released from the core would cause a rapid growth of radiation fields outside the core.